Effect of strong electrolytes on surface activity of aqueous 1,1-dimethyl-1-alkylhydrazinium chloride in aqueous solutions

The effect of electrolytes on the surface activity of aqueous anionic (1,1-dimethyl-1-alkylhydrazinium chloride homologues with the C₁₀–C₁₈ alkyl radical) and nonionic (Neonol AF 9–12) surfactants in aqueous solutions was studied.     

Lamellar phase formation in catanionic mixtures of hydrogenated and fluorinated surfactants: a comparative study

The properties and phase behaviors of the catanionic mixtures consisting of tetradecyltrimetylammonium bromide (TTABr) and different anionic surfactants (i.e., sodium docanoate, C₁₀HOONa; sodium laurate, C₁₂HOONa; sodium perfluorodecanoate, C₁₀FOONa) were examined, in particular when the molar mixing ratio in the aqueous solution was exactly 1:1. Although the three inspected systems have identical head groups and counterions, they exhibited very different lamellar (L_α) phases. When using the hydrogenated surfactants, the C₁₀HOONa–TTABr system formed domain-like L_α/L₁ two phases and the C₁₂HOONa–TTABr system formed cream-like L_α/L₁ two phases, respectively. In the case of the perfluorinated surfactant, the C₁₀FOONa–TTABr system formed interdigitated and tilted L_α gel. The microstructures of the three L_α phases were characterized by polarized microscope, freeze-fracture transmission electron microscope, small angle X-ray scattering, and X-ray diffraction. The phase transition of the lamellar gel at different temperature was studied by differential scanning calorimetry and rheological measurements. The results elucidated the formation of the L_α phase in catanionic mixtures containing hydrogenated or fluorinated anionic surfactants with molar mixing ratio of 1:1.     

Novel Cationic Gemini Surfactants Based on Piperazine: Synthesis,Surface Activity,and Foam Ability

A series of novel Gemini surfactants C_n-pi-C_n with piperazine moiety as spacer was synthesized and characterized by IR, ¹H NMR, and mass spectra. Their surface activities were evaluated by surface tension, electrical conductivity, and steady-state fluorescence. The obtained results indicated that the synthesized Gemini surfactants exhibited lower critical micelle concentration (cmc) and surface tension (γ_cmc) compared with traditional surfactants. The steady-state fluorescence measurement and electrical conductivity were recorded to demonstrate the accuracy of cmc values. In addition, the micellization was evaluated using conductivity measurement in the temperature range of 298–308 K. The foamability and foam stability of these Gemini surfactants were also examined. In which, the Gemini surfactant with the shortest chain (C₁₂) showed the best foamability but the poorest foam stability. Hydrophile–lipophile balance and emulsifying ability were studied and a comparatively poor emulsifying ability displayed.     

Effect of Organic Counterions on the Properties of N-Lauryl Diisopropanolamine Surfactants

The influence of counterions on the surface properties of N-lauryl diisopropanolamine surfactants is delineated using conductometry and surface tension measurements. Twelve types of organic counterions have been studied: C₁–C₁₂ monocarboxylic acids anions. The surface properties of the synthesized surfactants, including surface tension, critical micelle concentration (CMC), effectiveness (π_CMC), efficiency (pC₂₀), maximum surface excess (Γ_max), minimum surface area (A_min), Gibbs energy of micellization (ΔG_mic), and adsorption (ΔG_ad) processes in the aqueous. The biodegradability of the prepared surfactants was tested in river water using the die-away method. Petroleum-collecting and petroleum-dispersing capacities of the synthesized compounds on the surface of water of varying mineralization degree have been studied.     

Interfacial dilational properties of anionic gemini surfactants with polymethylene spacers

The dilational properties of anionic gemini surfactants alkanediyl-α,ω-bis(m-octylphenoxy sulfonate) (C₈C_mC₈) with polymethylene spacers at the water–air and water–decane interfaces were investigated by oscillating barriers and interfacial tension relaxation methods. The influences of oscillating frequency and bulk concentration on the dilational properties were explored. The experimental results show that the linking spacer plays an important role in the interfacial dilational properties. The moduli pass through one maximum for all three gemini surfactants at both water–air and water–decane interfaces. However, the values of moduli at the water–air interface are obviously higher than those at the water–decane interface because the sublayer formed by spacer chains will be destroyed by the insertion of oil molecules. Moreover, with the increase of spacer length, the surface adsorption film becomes more viscous at high concentration, which can be attributed to the process involving the formation of the sublayer. On the other hand, the spacers of the adsorbed C₈C₆C₈ molecules will extend into the oil phase when the interface is compressed. As a result, the interfacial film becomes more elastic with the increase of spacer length at high concentration. The experimental results obtained by the interfacial tension relaxation measurements are in accord with those obtained by the oscillating barriers method.     

Hemiesters and hemiamides of maleic and succinic acid: synthesis and application of surfactants in emulsion polymerization with styrene and butyl acrylate

Hemiesters and hemiamides of maleic acid with different chain lengths of the hydrophobic alkyl group (R = C₈H₁₇, C₁₀H₂₁, C₁₂H₂₅, C₁₆H₃₃) have been synthesized and used as surfactants in the emulsion polymerization of styrene and butyl acrylate. The same polymerization experiments were also carried out using nonreactive surfactants with an analogous succinic structure. The chemical structure of the surfactants was confirmed by 1H nuclear magnetic resonance. The melting point and critical micelle concentration of the reactive surfactants described herein were measured. All of the surfactants studied provided good stability of styrene/butyl acrylate latexes, when compared with a reference latex of a styrene/butyl acrylate copolymer prepared with a surfactant sodium dodecyl sulfate. The amount of surfactant grafted onto the particles of the final latex was estimated by conductimetric titration. Between 33 and 68% of surfactant used in emulsion polymerization was found on the surface of latex particles. Electrolyte addition at high concentration and freeze/thaw cycle cause flocculation of latexes. Copyright © 1999 John Wiley & Sons, Ltd.     

Magnetically Alignable Bicelles with Unprecedented Stability Using Tunable Surfactants Derived from Cholic Acid

Five novel surfactants were prepared by modifying the three hydroxy groups of sodium cholate with triethylene glycol chains endcapped with an amide ( SC‐C₁ , SC‐ ⁿ C₄ , and SC‐ ⁿ C₅ ) or a carbamoyl group ( SC‐O ⁿ C₄ and SC‐O ^t C₄ ). The phase behavior of aqueous mixtures of these surfactants with 1,2‐dimyristoyl‐sn‐glycero‐3‐phosphatidylcholine (DMPC) was systematically studied by ³¹P NMR spectroscopy. The surfactants endcapped with carbamate groups ( SC‐O ⁿ C₄ and SC‐O ^t C₄ ) formed magnetically alignable bicelles over unprecedentedly wide ranges of conditions, in terms of temperature (from 21–23 to >90 °C), lipid/surfactant ratio (from 5 to 8), total lipid content (5–20 wt %), and lipid type [DMPC, 1,2‐dilauroyl‐sn‐glycero‐3‐phosphatidylcholine (DLPC), or 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphatidylcholine (POPC)]. In conjunction with appropriate phospholipids, the carbamate‐endcapped surfactants afforded unique bicelles, characterized by exceptional thermal stabilities (from 0 to >90 °C), biomimetic lipid compositions (DMPC/POPC=25:75 to 50:50), and extremely large ²H quadrupole splittings (up to 71 Hz).     

The influence of mixed cationic–anionic surfactants on the three-phase contact parameters in silica–solution systems

The formation of thin wetting films on silica surface from aqueous solution of (a) tetradecyltrimetilammonium bromide (C₁₄TAB) and (b) surfactant mixture of the cationic C₁₄TAB with the anionic sodium alkyl- (straight chain C₁₂–, C₁₄– and C₁₆–) sulfonates, was studied using the microscopic thin wetting film method developed by Platikanov. Film lifetimes, three-phase contact (TPC) expansion rates, receding contact angles and surface tension were measured. It was found that the mixed surfactants caused lower contact angles, lower rates of the thin aqueous film rupture and longer film lifetimes, as compared to the pure C₁₄TAB. This behavior was explained by the strong initial adsorption of interfacial complexes from the mixed surfactant system at the air/solution interface, followed by adsorption at the silica interface. The formation of the interfacial complexes at the air/solution interface was proved by means of the surface tension data. It was also shown, that the chain length compatibility between the anionic and cationic surfactants controls the strength of the interfacial complex and causes synergistic lowering in the surface tension. The film rupture mechanism was explained by the heterocoagulation mechanism between the positively charged air/solution interface and the solution/silica interface, which remained negatively charged.     

Mechanism of electroless deposition of Ni–W–P alloys by adding surfactants

This paper describes an electroless deposition method for the formation of a thin metallic film containing mainly nickel with significant amounts of tungsten (up to 25%) and phosphorus (5–10%). The film was deposited from an aqueous electrolyte that contained sodium tungstate as a source of tungsten, nickel sulphate as a source of nickel and hypophosphite as the reducing agent and a source of phosphorus. The surfactants were p‐hexyloxy‐p‐sodium sulphonate azobenzene (HSA) with the formula H₁₃C₆OC₆H₄N₂ C₆H₄SO₃Na and p‐hexylbenzyltriethanol ammonium chloride (HBC) with the formula H₁₃C₆H₄CH₂N⁺ (C₂H₄OH)₃Cl^?, added as stabilizers. In this study the process parameters of typical solutions, such as temperature, pH and concentration of tungstate salt and the concentration of different surfactants, were presented and discussed. Adsorption of the surfactants on a metal surface was dependent, among other things, on the structure of their hydrophobic and hydrophilic portions. The effect of adsorption of these surfactants on a metal surface was examined above and below the critical micelle concentration (CMC). The deposition process involves several reactions that occur simultaneously and are described in detail in this work. The mechanism for interaction of the surfactants with the steel surface was proposed through the isotherm for adsorption from aqueous solution. Furthermore, the surface properties of the surfactants were measured, particularly the CMC, the surface tension reduction and the maximum surface excess Γ_max. The tungsten percentage in the deposit layer was strongly influenced by the plating conditions and the critical concentration of each surfactant. The results were discussed according to the surface properties of the additive. The thin film of Ni–W–P achieved high crystal refinement and high hardness, it was smooth and uniform and it exhibited superior corrosion resistance. Copyright © 2003 John Wiley & Sons, Ltd.     

Micellization and Interaction Properties of Aqueous Solutions of Mixed Cationic and Nonionic Surfactants

The micellization process of binary surfactant mixtures containing cationic surfactants viz. dodecyl pyridinium halide (C₁₂PyX; X=Cl, Br, I), tetradecyl pyridium bromide (C₁₄PyBr), and hexadecyl pyridium halide (C₁₆PyX; X=Cl, Br) and a nonionic surfactants viz. dodecyl nonapolyethylene glycol ether (C₁₂E₉), dodecyl decapolyethylene glycol ether (C₁₂E₁₀), dodecyl dodecapolyethylene glycol ether (C₁₂E₁₂), and dodecyl pentadecapolyethylene glycol ether (C₁₂E₁₅) in water at different mole fractions (0–1) were studied by surface tension method. The composition of mixed micelles and the interaction parameter, β evaluated from the CMC data obtained by surface tension for different systems using Rubingh's theory were discussed. Activity coefficient (f₁ and f₂) of cationic surfactant (C_nPyBr)/C₁₂E_m (n=12, 14, 16 and m=10, 12, 15) mixed surfactant systems were evaluated, which shows extent of ideality of individual surfactant in mixed system. The stability factors for mixed micelles were also discussed by Maeda's approach, which was justified on the basis of steric factor due to difference in head group of nonionic surfactant.     

Properties of two polymerizable surfactants aqueous solutions: dodecylethylmethacrylatedimethylammonium bromide and hexadecylethylmethacrylatedimethylammonium bromide. I. Critical micelle concentration

The aggregation of two polymerisable surfactants dodecylethylmethacrylatedimethylammonium bromide (C₁₂PS) and hexadecylethylmethacrylatedimethylammonium bromide (C₁₆PS) was studied with a battery of methods. Both surfactants form premicelles at low concentration, and show a critical micelle concentration and a transition between spherical and rod-like micelles. The micelle ionization degree and the adsorption at the air/solution interface were also studied. Results are interpreted on the basis of the conformation of the polar head group.     

Alkyl polyglucoside microemulsion phase behavior

We review several key elements of alkyl polyglucoside (C_mG_n) microemulsion phase behavior. The low solubility of C_mG_n surfactants in oils such as alkanes makes producing C_mG_n microemulsions and subsequent study of their phase behavior difficult. Increasing the solubility of C_mG_n in oil is therefore helpful for the systematic study of C_mG_n-based microemulsion formulations. To this end, the role of cosurfactants in producing microemulsions with water, alkanes, and n-alkyl β-d-glucopyranosides is first discussed. Adding C₁₀βG₁ to mixtures of water–alkane–ethoxylated alcohol surfactants (C_iE_j) produces a region of the three-phase body (a ‘chimney’) that is independent of temperature; thus C_mβG₁ are not completely soluble in the co-oil formed of alkane and C_iE_j at higher temperatures. Then, through a novel approach using oxygenated ether oils (C_kOC₂OC_k), microemulsions are formed with water, C_kOC₂OC_k, and C_mβG₁ and the phase behavior studied as a function of temperature and composition. Increased C_mβG₁ solubility in the more hydrophilic ether oils produces patterns of phase behavior in water–C_kOC₂OC_k–C_mβG₁ mixtures that are identical to those observed in water–alkane–C_iE_j mixtures. Using the water–ether oil–C_mβG₁ mixtures as a base case, the role of C_mG_n surfactant structure in setting C_mG_n microemulsion phase behavior is explored. The solubility of the α-d anomer (n-alkyl α-d-glucopyranosides, C_mαG₁) in water is much less than that of the β-d surfactant, and these solubility boundaries extend to high surfactant and oil concentrations in water–C_kOC₂OC_k–C_mαG₁ mixtures. Adding C_mG₂ compounds to water–C_kOC₂OC_k–C_mβG₁ mixtures shifts the phase behavior to high temperatures, again demonstrating the extreme hydrophilic nature of the sugar headgroup. Finally, adding small amounts of ionic alkyl sulfate surfactants to water–C_kOC₂OC_k–C_mβG₁ mixtures dramatically reduces the total amount of surfactant needed to form a single-phase microemulsion.     

Micellar and Mixed-Micellar Effects on Alkaline Hydrolysis of tris(1,10–phenanthroline)iron(II): Kinetic Exploration

The kinetics of alkaline hydrolysis of tris(1,10–phenanthroline)iron(II) has been studied in the presence of nonionic and mixed nonionic–ionic micellar media at 308 K. The effects of mixed-micellar environments of nonionic with ionic surfactants (C₁₂E₂₃/ATABs and C₁₂E₂₃/SDS) on the hydrolytic rate have been studied. The rate decreases monotonically with an increment of [C₁₂E₂₃]_T (total Brij 35 concentration) at constant [^?OH]₀ and has been discussed with the pseudo-phase micellar model. The rate also decreases with [C₁₂E₂₃]_T at a continuous addition of ionic surfactants (ATABs and SDS). The observed rate constant k_obs follows the empirical relation: k_obs = (k₀ + θK [C₁₂E₂₃]_T)/(1 + K [C₁₂E₂₃]_T) (where θ and K are empirical constants). The values of θ remain unaffected, whereas K decreases nonlinearly with [ATABs]_T in a mixed C₁₂E₂₃?ATAB micellar system. But the k_obs in a mixed C₁₂E₂₃–SDS micellar system is much lower than that of the C₁₂E₂₃–ATAB system and do not comply with any micellar kinetic models.     

Effect of Alkyl Chain Length on the Interfacial Dilational Properties of Hydroxy-Substituted Alkyl Benzenesulfonates

Dilational rheological behaviors of adsorption layers of three surfactants, sodium 2-hydroxy-3,5-dioctyl benzene sulfonate (C₈C₈), sodium 2-hydroxy-3-octyl-5-decyl benzene sulfonate (C₈C₁₀), and sodium 2-hydroxy-3-octyl-5-dodecylbenzenesulfonate (C₈C₁₂) formed at air–water and decane–water interfaces, have been investigated as a function of concentration and frequency (0.002–0.1 Hz) by the oscillating bubble/drop method. The experimental results show that the dilational moduli of hydroxy-substituted alkyl benzenesulfonates are obviously higher than those of the common surfactants, because the interfacial interactions between alkyl chains are improved drastically by the unique arrangement of C₈C₈ molecules at the interface. However, the moduli at the decane–water interface are much lower than those at the surfaces because decane molecules will insert into the surfactant molecules adsorbed at the interface and destroy the interactions between alkyl chains. With an increase in the number of carbon atom of 5-alkyl, the surface dilational modulus decreases because the orientation of the surfactant molecules at the surface varies from parallel to tilt. On the other hand, the diffusion-exchange process dominates the interfacial behavior and the interfacial modulus improves with the increase in the length of the alkyl chain.     

Interactions between ethyl(hydroxyethyl) cellulose and lysine-based surfactants in aqueous media

In this work, the interaction between ethyl(hydroxyethyl) cellulose (EHEC) and three dimeric lysine-based surfactants of distinct chain length (C₆, C₈ and C₁₀) have been assessed and the system was evaluated in terms of its temperature-dependent gelling capacity. The viscosity profile depends on the specific surfactant, its concentration and temperature. The observed profiles reflected polymer–polymer associations at elevated temperatures and polymer-surfactant interactions, implying the formation of micellar-type associations. The systems induce gelation at higher temperatures. Longer chain-length surfactants induce gelation at lower concentrations due to their stronger tendency to self-assemble. The thermo-responsive gels showed gel strength generally lower than 20 Pa.sⁿ and a fractal dimension of 2.3–2.4, respectively, indicating the formation of soft gels comprising a tight and homogeneous network. The weakest gel was produced in the presence of the C₆ surfactant. 2D Small-Angle Light Scattering patterns showed a pronounced effect of temperature in terms of the evolution of large hydrophobic clusters, an event precluded when high concentrations of the longer chain surfactants were used.     

Three-phase contact parameters measurements for silica-mixed cationic–anionic surfactant systems

The stability and interactions in thin wetting films between the silica surface and air bubble containing (a) straight chain C₁₀ amine and (b) cationic/anionic surfactant mixture of a straight chain C₁₀ amine with sodium C₈, C₁₀ and (straight chain) C₁₂ sulfonates, were studied using the microscopic thin wetting film method developed by Platikanov [D. Platikanov, J. Phys. Chem. 68 (1964) 3619]. Film lifetimes, three-phase contact (TPC) expansion rate, receding contact angles and surface tension were measured. The presence of the mixed cationic/anionic surfactants was found to lessen contact angles and suppresses the thin aqueous film rupture, thus inducing longer film lifetime, as compared to the pure amine system. In the case of mixed surfactants heterocoagulation could arise through the formation of positively charged interfacial complexes. Mixed solution of cationic and anionic surfactants shows synergistic lowering in surface tension. The formation of the interfacial complex at the air/solution interface was confirmed by surface tension data. It was also shown, that the chain length compatibility between the anionic and cationic surfactants system controls the strength of the interfacial complex. The observed phenomena were discussed in terms of the electrostatic heterocoagulation theory, where the interactions can be attractive or repulsive depending on the different surface activity and charge of the respective surfactants at the two interfaces.     

Studies on Interaction of Hydrophobically Modified Polyacrylamide of a New Family with Cationic Gemini Surfactant

A new family of hydrophobically modified polyacrylamides (HMPAM) was synthesized via homogeneous copolymerization of acrylamide (AM) and anionic surface-active monomer of acrylamide-type, sodium 2-acrylamido-tetradecane sulfonate (NaAMC₁₄S) in aqueous solution. The copolymers NaAMC₁₄S/AM with microblock structures and with different chain microstructures were obtained by varying the copolymerization factors, such as the feed ratio of NaAMC₁₄S to AM and the amount of added electrolyte NaCl and initiator. The interaction between copolymers NaAMC₁₄S/AM and cationic gemini surfactants, C₁₂C₃C₁₂Br₂ and C₁₂C₆C₁₂Br₂, was studied by using viscosimetry and fluorescent probe technique. The results show this new family of HMPAM, NaAMC₁₄S/AM, has very strong interaction with gemini surfactants, and their aqueous solutions exhibit unique rheological properties.     

Density and viscosity studies of poly(ethylene-oxide) alkyl alcohols

Density and viscosity of binary systems water-nonionic surfactants poly(ethylen-oxide) alkyl alcohols type, [C_nH_2n+1(OCH₂CH₂)_mOH, C_nE_m], have been studied. The partial molar volumes in the dilute solution range and the viscosity B-coefficients were calculated. The nonionic surfactants partial molar volumes were compared with those of ethylene glycol and poly(ethylenglycol) (PEG). The comparison shows that the ethoxy unit volume, (OCH₂CH₂), seems to be independent of the particular system. The consequences of this are discussed. A model for interpreting the experimental B values has been proposed. The model treats the macroscopic viscosity as the superimposition of different local effects. The following surfactants have been considered: C₅E₁, C₅E₂, C₆E₁, C₆E₂, C₆E₃, C₆E₄.     

Effect of Polymer on Dynamic Interfacial Tensions of Anionic–nonionic Surfactant Solutions

The dynamic interfacial tensions (IFTs) of enhanced oil recovery (EOR) surfactant/polymer systems against n-decane have been investigated using a spinning drop interfacial tensiometer in this paper. Two anionic–nonionic surfactants with different hydrophilic groups, C₈PO₆EO₃S (6-3) and C₈PO₆EO₆S (6-6), were selected as model surfactants. Partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were employed. The influences of surfactant concentration, temperature, polymer concentration, and oleic acid in the oil on IFTs have been studied. The experimental results show that anionic–nonionic surfactants can form compact adsorption films and reach ultralow IFT (10^?3 mN/m) under optimum conditions. The addition of polymer has great influence on dynamic IFTs between surfactant solutions and n-decane mainly by the formation of looser mixed films resulting from the penetration of polymer chains into the interface. The compact surfactant film will also be weakened by the competitive adsorption of oleic acid, which results in the increase of IFT. Moreover, the penetration of polymer chains will be further destroyed surfactant/polymer mixed layer and lead to the obvious increase of IFT. On the other hand, polymers show little effect on the IFTs of 6-6 systems than those of 6-3 because of the hindrance of longer EO chain of 6-6 at the interface.     

Salt effects on the aggregation behavior of tripolar zwitterionic surfactants with different inter-charge spacers in aqueous solution

Salt effects on the aggregation behavior of tripolar zwitterionic surfactants in aqueous solutions have been investigated using surface tension, dynamic light scattering (DLS), freeze-fracture transmission electron microscopy (FF-TEM), and ¹H NMR. The tripolar zwitterionic surfactants with different inter-charge spacers are [C₁₄H₂₉(CH₃)₂N⁺C_sN⁺(CH₃)₂CH₂CH₂CH₂SO₃ ^?]Br^? (C₁₄C_sTri, C_s?=?–(CH₂)₂–, –(CH₂)₆–, –(CH₂)₁₀–, and p-xylyl). It is found that the critical micelle concentration (CMC) values of the corresponding traditional zwitterionic surfactant C₁₄H₂₉(CH₃)₂N⁺CH₂CH₂CH₂SO₃ ^? (TPS) are almost constant with the increase of the NaBr concentration. However, the CMC values of C₁₄C_sTri decrease sharply at a lower NaBr concentration and then level off at a higher NaBr concentration. Moreover, the decreasing extents of the CMC values for C₁₄C₂Tri, C₁₄C₆Tri, and C₁₄C_pxTri are very close, but more significant than that for C₁₄C₁₀Tri, suggesting that the self-assembly ability of the tripolar zwitterionic surfactants with a longer inter-charge spacer is less sensitive to NaBr. The DLS and FF-TEM results reveal that C₁₄C₂Tri, C₁₄C₆Tri, and C₁₄C_pxTri form micelles without NaBr and that the size slightly increases with the increase of NaBr concentration, whereas micelles and vesicles coexist for C₁₄C₁₀Tri and TPS without NaBr and then transfer to micelles upon the addition of NaBr. The salt-induced morphological transition for C₁₄C₁₀Tri is further studied using ¹H NMR. The addition of NaBr reduces both the electrostatic repulsion between the same charged ammoniums and the electrostatic attraction between the oppositely charged ammonium and sulfonate. Thus, the longer inter-charge spacer of C₁₄C₁₀Tri tends to be more bended and the sulfonate group becomes available to contact the ammonium, which promotes micellization.